The present invention relates to fuel cells assembled together to form a fuel cell power plant suited for usage in transportation vehicles, portable power plants, or as stationary power plants, and the invention especially relates to a fuel cell power plant that utilizes an antifreeze solution passing through the plant to remove heat.
Fuel cell power plants are well-known and are commonly used to produce electrical energy from reducing and oxidizing fluids to power electrical apparatus such as apparatus on-board space vehicles. In such power plants, a plurality of planar fuel cells are typically arranged in a stack surrounded by an electrically insulating frame structure that defines manifolds for directing flow of reducing, oxidant, coolant and product fluids. Each individual cell generally includes an anode electrode and a cathode electrode separated by an electrolyte. A reactant or reducing fluid such as hydrogen is supplied to the anode electrode, and an oxidant such as oxygen or air is supplied to the cathode electrode. In a cell utilizing a proton exchange membrane (xe2x80x9cPEMxe2x80x9d) as the electrolyte, the hydrogen electrochemically reacts at a surface of the anode electrode to produce hydrogen ions and electrons. The electrons are conducted to an external load circuit and then returned to the cathode electrode, while the hydrogen ions transfer through the electrolyte to the cathode electrode, where they react with the oxidant and electrons to produce water and release thermal energy.
The anode and cathode electrodes of such fuel cells are separated by different types of electrolytes depending on operating requirements and limitations of the working environment of the fuel cell. One such electrolyte is the aforesaid proton exchange membrane (xe2x80x9cPEMxe2x80x9d) electrolyte, which consists of a solid polymer well-known in the art. Other common electrolytes used in fuel cells include phosphoric acid or potassium hydroxide held within a porous, non-conductive matrix between the anode and cathode electrodes. It has been found that PEM cells have substantial advantages over cells with liquid acid or alkaline electrolytes in satisfying specific operating parameters because the membrane of the PEM provides a barrier between the reducing fluid and oxidant that is more tolerant to pressure differentials than a liquid electrolyte held by capillary forces within a porous matrix. Additionally, the PEM electrolyte is fixed, and cannot be leached from the cell, and the membrane has a relatively stable capacity for water retention.
Manufacture of fuel cells utilizing PEM electrolytes typically involves securing an appropriate first catalyst layer, such as a platinum alloy, between a first surface of the PEM and a first or anode porous substrate layer to form an anode electrode adjacent the first surface of the PEM, and securing a second catalyst layer between a second surface of the PEM opposed to the first surface and a second or cathode porous substrate layer to form a cathode electrode on the opposed second surface of the PEM. The anode catalyst, PEM, and cathode catalyst secured in such a manner are well-known in the art, and are frequently referred to as a xe2x80x9cmembrane electrode assemblyxe2x80x9d, or xe2x80x9cM.E.A.xe2x80x9d, and will be referred to herein as a membrane electrode assembly. In operation of PEM fuel cells, the membrane is saturated with water, and the anode electrode adjacent the membrane must remain wet. As hydrogen ions produced at the anode electrode transfer through the electrolyte, they drag water molecules in the form of hydronium ions with them from the anode to the cathode electrode or catalyst. Water also transfers back to the anode from the cathode by osmosis. Product water formed at the cathode electrode is removed from the cell by evaporation or entrainment into a gaseous stream of either the process oxidant or reducing fluid. In fuel cells containing porous reactant flow fields, as described in U.S. Pat. No. 4,769,297, owned by the assignee of all rights in the present invention, a portion of the water maybe alternatively removed as a liquid through the porous reactant flow field to a circulating cooling fluid.
While having important advantages, PEM cells are also known to have significant limitations especially related to liquid water transport to, through and away from the PEM, and related to simultaneous transport of gaseous reducing fluids and process oxidant fluids to and from the electrodes adjacent opposed surfaces of the PEM. The prior art includes many efforts to minimize the effect of those limitations. Use of such fuel cells assembled together in a well known fuel cell stack with additional components to form a fuel cell power plant in order to power a transportation vehicle gives rise to additional problems associated with water management, such as preventing the product water from freezing, and rapidly melting any frozen water during start up whenever the fuel-cell powered vehicle is operated in sub-freezing conditions. Known fuel cell power plants typically utilize a coolant or thermal management system supplying a flow of cooling fluid through the fuel cell and other plant components to maintain the cell within an optimal temperature range and efficiently distribute heat. Where the cooling fluid is a solution including water it also must be kept from freezing. It is known to utilize an antifreeze solution such as ethylene glycol and water or propylene glycol and water as a cooling fluid in such coolant systems.
However, such antifreeze solutions are known to be adsorbed by and poison the catalysts that form electrodes. Furthermore, those antifreeze solutions have low surface tensions which results in the solutions wetting any wetproofed support layers adjacent cell catalysts, thereby impeding diffusion of reactant fluids to the catalysts, which further decreases performance of the electrodes. Also, the vapor pressure of those antifreezes is too high, resulting in excessive loss rates of the antifreeze solutions through fuel cell exhaust streams or from steam produced in boilers of fuel processing components of fuel cell power plants. Therefore coolant systems of fuel cells that utilize an antifreeze solution are known to be sealed from the electrodes, so that the solution is not in direct fluid communication with the electrodes.
Sealing the coolant system from direct fluid communication with the cell and hence with the product water formed at the cathode electrode results in decreased cell performance due to less efficient removal of the product water. Fuel cell power plants that utilize sealed coolant plates typically remove product water as an entrained liquid. This requires a tortuous serpentine flow path with a resultant high pressure drop. An example of such a cell is shown in U.S. Pat. No. 5,773,160. That type of cell is not suitable for operating at near ambient reactant pressures which is a preferred operating pressure for many fuel cell systems. The decreased performance of cells with sealed coolant plates requires that additional cells be used to satisfy the design power requirement. The additional cells combined with heavier, sealed coolers results in an increase in weight and volume of a fuel cell power plant which is undesirable for powering a vehicle.
Additionally, where a fuel cell power plant powers a vehicle, the atmosphere serving as a process oxidant stream directed into contact with the cathode electrode will vary significantly in humidity. Consequently, it is known to undertake substantial efforts to humidify the process oxidant and reducing fluid streams in order to minimize water loss from the PEM electrolyte. Known efforts include recycling some of the product water from the cell, and/or directing some of the cooling fluid within the coolant system as a vapor into the process oxidant and/or reducing fluid streams entering the fuel cell. However, with known fuel cells, the humidity enhancing fluid must be free of any antifreeze solutions in order to prevent the antifreeze from poisoning the catalysts. Known fuel cells utilize sealed coolant systems that are isolated from humidification systems, or for example, one known fuel cell humidification systems utilizes complex, heavy and large membrane barrier components consisting of uncatalyzed PEM cells upstream of catalyzed cells in order to isolate any antifreeze solution within the cooling fluid or within the product water mixed with cooling fluid from contact with the electrode catalysts. Such efforts to isolate the antifreeze solution add to the cost, weight and volume of the fuel cell.
A further problem associated with cooling fuel cells wherein the coolant fluid contacts cell components is limiting conductivity of the coolant fluid to avoid shunt current corrosion that results from a conductive coolant fluid providing a conductive bridge between electrically insulated cell components. Where the cooling fluid includes water, or similar solvents dissolved metals and other ions must be removed, such as by passing the cooling fluid through, a demineralizer as shown in U.S. Pat. No. 4,344,850 to Grasso, which Patent is owned by the assignee of all rights in the present invention, and which Patent is hereby incorporated herein by reference. However, when such a demineralizer or similar water treatment system is utilized within a fuel cell power plant in a vehicle, the cooling fluid within the water treatment system components must also be protected against freezing. If the cooling fluid were to freeze, it could cause mechanical damage to components of a water treatment system such as a demineralizer; it would require melting during a start-up procedure; and, where a demineralizer includes ion exchange resin beads, the freezing and thawing cooling fluid could cause break up of the beads, resulting in a high pressure drop and impeded flow within the demineralizer. Consequently, the water treatment system for treating the cooling fluid must be freeze protected without adding significant further weight and cost to the fuel cell power plant.
Accordingly there is a need for a fuel cell power plant that may be operated in sub-freezing conditions that does not require isolating an antifreeze cooling fluid from the cathode and anode electrodes within a sealed coolant system; that minimizes free water within the system that may be frozen when the fuel cell is not operated while subjected to sub-freezing temperatures; and that does not require significant increases in weight, volume or cost of the plant.
A direct antifreeze cooled fuel cell power plant is disclosed for producing electrical energy from reducing and process oxidant fluid streams. The plant includes at least one fuel cell for producing electrical energy from the reducing and oxidant fluid streams; a thermal management system that directs flow of a cooling fluid for controlling heat within the plant including a porous water transport plate adjacent and in fluid communication with a cathode flow field of the fuel cell and including a direct antifreeze solution passing through the water transport plate; a direct mass and heat transfer device secured in fluid communication with both an oxidant inlet that directs the oxidant fluid in a process oxidant stream into the fuel cell and also with a plant exhaust passage so that the device directly transfers through a mass transfer medium mass and heat such as water exiting the plant in a plant exhaust stream within the plant exhaust passage back into the plant within the process oxidant stream, wherein the mass transfer medium may be the cooling fluid directed from the thermal management system to pass through the direct mass and heat transfer device.
In a first alternative embodiment, the direct antifreeze cooled fuel cell power plant may include an anode exhaust burner that receives and burns an anode exhaust stream exiting the fuel cell and then directs the burned anode exhaust stream into the plant exhaust passage and direct mass and heat transfer device so that moisture and heat in the burned anode exhaust transfer into the process oxidant stream. In a second alternative embodiment, the plant includes a steam injection system having a boiler that receives heat from the anode exhaust burner and that is in fluid communication with the cooling fluid so that the boiler generates low pressure steam from the cooling fluid for injection into the reducing fluid stream within a reducing fluid inlet passage upstream of the fuel cell to humidify the reducing fluid, and wherein the boiler also serves to evaporate excess water out of the cooling fluid to thereby control a concentration of the direct antifreeze in the cooling fluid. In an additional embodiment, the direct antifreeze cooled fuel cell power plant includes a water treatment system having a demineralizer in fluid communication with the cooling fluid, and having a degasifier also in fluid communication with the cooling fluid that passes the cooling fluid in mass transfer relationship with the process oxidant stream so that dissolved gases in the cooling fluid transfer from the cooling fluid into the process oxidant stream.
The direct antifreeze solution of the invention may be any organic antifreeze solution that is non-volatile at cell operating temperatures. For purposes herein, xe2x80x9cnon-volatilexe2x80x9d is defined to mean that the antifreeze solution sustains a loss of less than 10% of its antifreeze for every 500 operating hours of the fuel cell power plant at fuel cell operating temperatures. Alternatively, a first preferred direct antifreeze solution may be a special direct antifreeze solution having the following characteristics: 1. a freezing point of at least xe2x88x9220 degrees Fahrenheit (hereafter xe2x80x9c0xc2x0 F.xe2x80x9d); 2. a surface tension greater than 60 dynes per centimeter (hereafter xe2x80x9cdyne/cmxe2x80x9d) at a cell operating temperature of about 150xc2x0 F.; 3. a partial pressure of antifreeze above the solution at about 150xc2x0 F. that is less than 0.005 mm of mercury (hereafter xe2x80x9cmm Hgxe2x80x9d); and, 4. that is capable of being oxidized by catalysts of the fuel cell at fuel cell voltages. A second preferred antifreeze solution may be an alkanetriol direct antifreeze solution, and in particular an alkanetriol selected from the group consisting of glycerol, butanetriol, and pentanetriol. The direct, special and alkanetriol direct antifreeze solutions minimize movement of the antifreeze as a vapor out of the water transport plate into contact with the cathode or anode catalysts, and also minimize direct antifreeze solution loss from the thermal management system, direct mass and heat transfer system, steam injection system, and water treatment system of the power plant as well as from any other fuel cell components such as the plant exhaust stream exiting the cell.
In an additional embodiment, the direct antifreeze solution passing through the water transport plate may be directed to flow at a pressure that is less than a pressure of the process reactant streams passing adjacent water transport plates. A preferred fuel cell operates at near ambient pressure and the process oxidant stream and reducing fluid stream are pressurized to 1 to 2 pounds per square inch gauge (hereafter xe2x80x9cPSIGxe2x80x9d) above ambient pressure, and the direct antifreeze solution is directed to flow through the water transport plate at about 1 to 2 PSIG below ambient pressure. Such a positive pressure differential between the process oxidant stream and the antifreeze solution within the water transport plate further assists movement of the product water formed at the cathode catalyst through the porous cathode substrate and into the water transport plate. The positive pressure differential also limits movement of any liquid antifreeze solution flowing within the water transport plate from flowing out of the water transport plate into the higher pressure process reactant streams passing within reactant flow fields defined adjacent to and/or within the porous cathode substrate.
Accordingly it is a general object of the present invention to provide a direct antifreeze cooled fuel cell power plant that overcomes deficiencies of the prior art.
It is a more specific object to provide a direct antifreeze cooled fuel cell power plant that eliminates need for a separate sealed thermal management system for operation in sub-freezing conditions.
It is yet another object to provide a direct antifreeze cooled fuel cell power plant that eliminates need for uncatalyzed membrane barrier components of a humidification system between an antifreeze cooling fluid and the fuel cell.
It is another object to provide a direct antifreeze cooled fuel cell power plant that minimizes free liquid water that may freeze when the fuel cell is not operating in sub-freezing conditions.
It is yet a further object to provide a direct antifreeze cooled fuel cell power plant that directly transfers mass and heat leaving the power plant back into the plant through a mass transfer medium supplied from a thermal management system.
It is another specific object to provide a direct antifreeze cooled fuel cell power plant that controls a concentration of a direct antifreeze within a cooling fluid through usage of a steam injection system that humidifies a reducing fluid stream.